EP1926163A1

EP1926163A1 - A negative active material, a method of preparing the same, and a rechargeable lithium battery including the same

Info

Publication number: EP1926163A1
Application number: EP07121149A
Authority: EP
Inventors: Kyoung-Han Yew; Nam-Soon Choi; Sung-Soo Kim; Su-Yeong Park
Original assignee: Samsung SDI Co Ltd
Current assignee: Samsung SDI Co Ltd
Priority date: 2006-11-22
Filing date: 2007-11-20
Publication date: 2008-05-28
Anticipated expiration: 2027-11-20
Also published as: KR100778450B1; JP2008130570A; JP4965412B2; EP1926163B1; US20080118834A1; CN101188287B; CN101188287A; US8835049B2

Abstract

A negative active material (10) for a rechargeable lithium battery includes a core (20) including an active material capable of performing reversible electrochemical oxidation and reduction, and a coating layer (30) on the surface of the core. The coating layer includes a reticular structure including -O-M-O- (31) wherein M is selected Si, Ti, Zr, Al, or combinations thereof and an organic functional group (32) linked to M as a side chain. The organic functional group is selected from the group consisting of an alkyl group, a haloalkyl group, a substituted or unsubstituted aryl group, and combinations thereof. The negative active material for a rechargeable lithium battery according to the present invention can be applied along with an aqueous binder, and improve high capacity, good cycle-life, and particularly high capacity during charge and discharge at a high rate.

Description

The present invention relates to a negative active material for a rechargeable lithium battery, a method of preparing the same, and a rechargeable lithium battery including the same.
A lithium rechargeable battery has recently drawn attention as a power source of a small portable electronic device. It uses an organic electrolyte solution and thereby has a discharge voltage that is twice as high as a conventional battery using an alkali aqueous solution, and accordingly has a high energy density.
A negative active material for a lithium battery can reversibly receive and supply lithium ions while maintaining its structural and electrical properties. For the negative active material, a lithium metal, a lithium-containing alloy, or a carbon-based material with a potential that is similar to lithium metal when lithium ions are intercalated/deintercalated is usually used. A battery using lithium metal or a lithium alloy as a negative active material is called a lithium metal battery, and a battery using a carbon material is called a lithium ion battery.
A lithium metal battery using lithium metal or a lithium alloy as its negative electrode has a risk of explosion due to a dendrite-short-circuit. Hence, the lithium metal battery is being replaced by a lithium ion battery that uses a carbon material as its negative active material and does not have such a risk. The lithium ion battery transfers only lithium ions during charge/ discharge, and it maintains the electrode active material as it is. Thus, the lithium ion battery has improved stability and cycle-life.
In the lithium ion battery, a non-aqueous system in which polyvinylidene fluoride (polyvinylidene difluoride or PVDF) is dissolved in N-methyl-2-pyrrolidone (NMP) or an organic acetone solvent is usually used as a binder for a conventional negative electrode plate. However, when the PVDF/NMP non-aqueous system is used as a binder, the organic solvent such as NMP and acetone may contaminate the natural environment. Also, since the organic solvent is expensive, the manufacturing cost for a lithium battery is increased. In addition, since most organic solvents are highly volatile, there is a risk of explosion when they are used in an enclosed space. To prevent explosions, an anti-explosion unit is additionally required.
To overcome the problems, researchers are actively studying to develop a method of using an aqueous system in which styrene-butadiene rubber (SBR) is dispersed in water along with a thickener, e.g., carboxymethylcellulose (CMC), when a negative electrode plate is manufactured. Since the SBR binder can be dispersed in water in the form of emulsion, it does not have to use an organic solvent, and the SBR binder has strong adherence. With the SBR binder, the amount of a binder is reduced and the amount of a negative active material is increased, which is advantageous in manufacturing a high-capacity lithium battery.
When an aqueous solvent is used with an aqueous binder, the high surface tension of the aqueous solvent deteriorates the coating property of a negative active material slurry to thereby reduce the planarity of a negative electrode. The low planarity of the negative electrode makes the surface of the negative electrode non-uniform to thereby reduce a reaction surface area and deteriorate the cycle-life characteristic.
The present invention provides a negative active material for a rechargeable lithium battery that can improve stability at the interface between a negative electrode and an electrolyte, be applied with an aqueous binder as well as a non-aqueous binder, and improve high capacity, good cycle-life, and particularly high capacity during charge and discharge at a high rate, and a method of preparing the negative active material.
The present invention also provides a rechargeable lithium battery including the negative active material and having high capacity and excellent cycle-life and particularly high capacity during charge and discharge at a high rate.
According to a first aspect of the present invention, there is provided a negative active material for a rechargeable lithium battery that includes a core including an active material capable of performing reversible electrochemical oxidation and reduction, and a coating layer on the surface of the core. The coating layer includes a reticular structure including - O-M-O- wherein M is selected from Si, Ti, Zr, Al, or combinations thereof, and an organic functional group linked to the M as a side chain.
The organic functional group is selected from the group consisting of an alkyl group, a haloalkyl group, a substituted or unsubstituted aryl group, and combinations thereof.
The substituted aryl group may be an aryl group substituted by at least one functional group selected from the group consisting of an alkyl group and a haloalkyl group.
The organic functional group may be selected from the group consisting of a C1 to C10 alkyl group, a C1 to C10 haloalkyl group, a C6 to C12 aryl group, a C6 to C12 aryl group substituted by at least one C1 to C10 alkyl group, a C6 to C12 aryl group substituted by at least one C1 to C10 haloalkyl group, and combinations thereof. The aryl group may be benzyl, phenyl, or tolyl.
The coating layer may have a thickness of 20 nm or less. According to one embodiment, the coating layer has a thickness of 10 nm or less. According to another embodiment, the coating layer has a thickness ranging from 5 to 10 nm.
The active material may be a material selected from the group consisting of a material capable of reversibly intercalating and deintercalating lithium ions, lithium metal, a lithium-containing alloy, and a material being capable of reversibly forming a lithium-containing compound by reacting with lithium ions.
The active material may be selected from the group consisting of crystalline carbon; amorphous carbon; Si, silicon oxide, Sn; tin oxide, a tin alloy composite, a transition element oxide, a lithium metal nitride, lithium vanadium oxide, and a lithium-containing alloy including at least one metal selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, Fe, Sn, and combinations thereof.
The active material may be a compound represented by the following Formula 1:

[Chemical Formula 1] Li_xM'_yV_zO_2+d

wherein, in the above formula, 0.1 ≤ x ≤ 2.5, 0 ≤ y ≤ 0.5, 0.5 ≤ z ≤ 1.5, 0 ≤ d ≤ 0.5, and M' is a metal selected from the group consisting of Al, Cr, Mo, Ti, W, Zr, and combinations thereof.
According to another aspect of the present invention, there is provided a method of making a negative active material for a rechargeable lithium battery that includes preparing a core liquid by mixing a core material (i.e., an active material) being capable of performing reversible electrochemical oxidation and reduction, an organic solvent, a base, and water; preparing a precursor liquid including an organic-inorganic hybrid precursor including the organic functional group, an organic solvent, and water; and mixing the core liquid and the precursor liquid.
The organic-inorganic hybrid precursor may be used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the core material. According to one embodiment, the organic-inorganic hybrid precursor is used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the core material. According to another embodiment, the organic-inorganic hybrid precursor is used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the core material.
The base may be aqueous ammonia. In an embodiment, the core material is used in an amount of 1 to 10 g per 1,000 ml of organic solvent(s) in the mixture of the core liquid and the precursor liquid, the base is used at a concentration of 0.05 to 1M, and the water is used at a concentration of 10 to 20M in the mixture of the core liquid and the precursor liquid.
According to yet another aspect of the present invention, there is provided a rechargeable lithium battery that includes a negative electrode including the negative active material, a positive electrode including a positive active material, and an electrolyte.
According to a further aspect of the present invention, there is provided the use of a negative active material according to the present invention in its first aspect for an electrode of a rechargeable lithium battery.
A more complete appreciation of the invention, and many of the attendant advantages thereof, will be readily apparent by reference to the following detailed description when considered in conjunction with the accompanying drawings, wherein:

FIGURE 1A and 1B schematically show a negative active material for a rechargeable lithium battery according to one embodiment of the present invention;
FIGURE 2 schematically shows a rechargeable lithium battery according to one embodiment of the present invention;
FIGURE 3 shows a spectrum of the negative active material according to Example 1 measured by a Fourier Transform Infrared (FT-IR) spectrometer; and
FIGURE 4 is a graph showing capacity retention of the cells according to Examples 2 and 4, and Comparative Examples 1 and 2 after 50 charges and discharges.

The present invention relates to a negative active material for a rechargeable lithium battery that has a core-shell structure.
The core includes an active material capable of performing reversible electrochemical oxidation and reduction. The active material may be a material selected from the group consisting of a material capable of reversibly intercalating and deintercalating lithium ions, lithium metal, a lithium-containing alloy, a material capable of reversibly forming a lithium-containing compound by reacting with lithium ions.
The material capable of reversibly intercalating and deintercalating lithium ions may be a generally-used carbon-based negative active material such as crystalline carbon, amorphous carbon, and combinations thereof.
The material capable of reversibly forming a lithium-containing compound by reacting with lithium ions may include Si, silicon oxide, Sn, tin oxide, a tin alloy composite, a transition element oxide, a lithium metal nitride, or a lithium metal oxide such as lithium vanadium oxide.
The lithium-containing alloy may be an alloy of lithium and a metal selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, Fe, and Sn.
According to one embodiment of the present invention, the active material is a compound represented by the following Formula 1:

[Chemical Formula 1] Li_xM'_yV_zO_2+d

wherein, in the above formula, 0.1 ≤ x ≤ 2.5, 0 ≤ y ≤ 0.5, 0.5 ≤ z ≤ 1.5, 0 ≤ d ≤ 0.5, and M' is a metal selected from the group consisting of Al, Cr, Mo, Ti, W, Zr, and combinations thereof.
The coating layer is disposed on the core, has a reticular structure, and includes a material including an element selected from the group consisting of Si, Ti, Zr, Al, and combinations thereof. In particular, the core is surrounded by a coating layer including -O-M-O-(wherein M is Si, Ti, Zr, or Al), and an organic functional group linked to the M as a side chain. The organic functional group is linked to M and does not link to the core.
The organic functional group is selected from the group consisting of an alkyl group, a haloalkyl group, a substituted or unsubstituted aryl group, and combinations thereof. The substituted aryl group may be an aryl substituted by a functional group selected from the group consisting of an alkyl group, a haloalkyl group, and combinations thereof. The aryl group may be benzyl, phenyl, or tolyl.
According to one embodiment of present invention, the organic functional group is selected from the group consisting of a C1 to C10 alkyl group, a C1 to C10 haloalkyl group, a C6 to C12 aryl group, a C6 to C12 aryl group substituted by at least one C1 to C10 alkyl group, a C6 to C12 aryl group substituted by at least one C1 to C10 haloalkyl group, a C6 to C12 aryl group substituted by at least one C1 to C10 haloalkyl group, and combinations thereof.
The coating layer has a nano-sized thickness that can conduct lithium ions, and does not incur resistance. According to one embodiment, the inorganic oxide coating layer has a thickness of 20 nm or less. According to another embodiment, the coating layer has a thickness of 10 nm or less. According to yet another embodiment, the coating layer has a thickness of 5 to 10 nm. When the coating layer has a thickness of more than 20 nm, it may act as a resistance layer to reduce transfer speed of electrons and lithium ions into the core active material, resulting in a significant decrease of electrochemical characteristic such as high rate characteristics, cycle-life, and so on.
FIGURE 1A schematically shows a negative active material for a rechargeable lithium battery according to one embodiment of the present invention.
As shown in FIGURE 1A, the active material 10 has a core-shell structure including the core 20 and the coating layer 30. FIGURE 1B is an enlarged view of the coating layer 30 of an exemplary negative active material. -O-M-O- linkages surround the surface of the core, and the organic functional group, X, is linked to M as a side chain. As shown in FIGURE 1B, the active material 10 includes -O-M-O- linkages having a reticular structure 31 disposed on the surface of the core 20, and the organic functional group 32 linked hereto.
An SEI (solid electrolyte interface) film is formed by electrochemical decomposition of an electrolyte at the interface between an electrolyte and a negative active material in a conventional battery system. According to one embodiment of the present invention, the - O-M-O- linkages are disposed on the surface of the core to minimize formation of an SEI film during charge and discharge and thereby improve reversible efficiency and cycle-life.
The negative active material according to one embodiment of the present invention is prepared as follows.
The core material, an organic solvent, a base, and water are mixed to prepare a core liquid. An organic-inorganic hybrid precursor, an organic solvent, and water are mixed to prepare a precursor liquid. Then the core liquid and the precursor liquid are mixed.
The core liquid and the precursor liquid can be used in an appropriate amount so that the core material might be in an amount of 1 to 10g per 1,000 ml of an organic solvent(s) in the mixture of the core liquid and the precursor liquid, 0.05 to 1M base, and 10 to 20M water in the mixture of the core liquid and the precursor liquid.
The core liquid and the precursor liquid can be mixed in an appropriate mixing ratio so that the component materials may be within the above range. The organic-inorganic hybrid precursor can be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the core material. According to one embodiment, the organic-inorganic hybrid precursor can be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the core material. According to another embodiment, the organic-inorganic hybrid precursor can be included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the core material. When an organic-inorganic hybrid precursor is included in an amount of less than 1 part by weight, the prepared coating layer may have little effect. On the contrary, when it is included in an amount of more than 30 parts by weight, a thick net-structured membrane is formed, increasing resistance of an electrode.
The core liquid is prepared by dispersing a core material into an organic solvent, and then adding a base and water to the mixture.
The core material includes the aforementioned active material.
The base plays a role of a catalyst promoting a reaction. It can include any base, so far as the base acts as a catalyst promoting a reaction. For example, it may include aqueous ammonia with pH 8 to 9.
The organic solvent may be selected from the group consisting of methanol, ethanol, propanol, isopropanol, and mixtures thereof.
The precursor liquid is prepared by mixing an organic-inorganic hybrid precursor, an organic solvent, and water. Herein, the organic solvent may be selected from the group consisting of methanol, ethanol, propanol, isopropanol, and mixtures thereof.
The organic-inorganic hybrid precursor may include at least two functional groups participating in a sol-gel reaction, and also one or two functional groups not participating in a sol-gel reaction, which are bound at M therein. According to one embodiment, it may include only one functional group not participating in sol-gel reaction.
The organic-inorganic hybrid precursor may include a compound represented by the following Formula 2:

[Chemical Formula 2] R₁-M-(OR₂)_n

wherein, in the above formula, M is selected from the group consisting of Si, Ti, Zr, and Al, R₁ is selected from the group consisting of an alkyl group, a haloalkyl group, a substituted or unsubstituted aryl group, and combinations thereof, R₂ is a C1 to C7 alkyl group, and n is determined according to a valence of M. According to one embodiment, n ranges from 1 to 6 and in another embodiment, n ranges from 1 to 4.
According to one embodiment of the present invention, R₁ is selected from the group consisting of a C1 to C10 alkyl group, a C1 to C10 haloalkyl group, a C6 to C12 aryl group, a C6 to C12 aryl group substituted by at least one C1 to C10 alkyl group, a C6 to C12 aryl group substituted by at least one C1 to C10 haloalkyl group, and combinations thereof, and R₂ is a C1 to C5 alkyl group.
The organic-inorganic hybrid precursor represented by the above Formula 2 may include a compound represented by the following Formula 2a.
In the above mixing process, when a precursor surrounds a core material, they simultaneously have hydrolysis and condensation reactions, through which a coating layer with a reticular structure is formed from the precursor on the surface of the core material.
Next, a solvent in the reaction is volatilized and then heat-treated, obtaining a negative active material according to the present invention.
Herein, the volatilization process is performed by heat-treating a dispersion at a temperature of 50 to 100 °C. According to another embodiment of the present invention, it may be performed at a temperature of 60 °C. The temperature for volatilization can be appropriately changed depending on kinds of alcohol used as a solvent of a dispersion. When the volatilization is performed at a temperature of lower than 50 °C, the volatilization process may become too long, while when at a temperature of higher than 100 °C, there may be no big different effects, compared with 100°C.
In addition, the heat treatment can be performed at a temperature of 300 to 600 °C. When the heat treatment is performed at a temperature of lower than 300 °C, impurities may remain inside a core material. On the contrary, when performed at a temperature of higher than 600 °C, it may not be economical.
The coating layer formed in this way may have a thickness of nanometers. According to one embodiment, it may have a thickness of less than 20 nm, and according to another embodiment, it may have a thickness ranging from 5 to 10 nm. When a coating layer includes an organic functional group, it may have increased miscibility with a binder, which will be used for preparing a composition for an electrode.
The rechargeable lithium battery includes a negative electrode including the above negative active material, a positive electrode, and an electrolyte.
The negative electrode includes a current collector and a negative active material layer disposed on the current collector. The negative active material layer includes the above negative active material.
The negative electrode may be fabricated as follows: a composition including the negative active material, a binder, and optionally a conductive agent which are mixed in a solvent is applied on a negative current collector such as copper.
The negative active material is the same as the above-described. According to one embodiment, the negative active material is included in an amount of 50 to 99 wt% based on the total weight of the negative active material layer. According to another embodiment, the negative active material is included in an amount of 80 to 98 wt% based on the total weight of the negative active material layer. When the amount of the negative active material is less than 50 wt%, battery capacity may be decreased, whereas when it is more than 99 wt%, the relative amount of binder is reduced and thus binding force between the negative active material layer and a current collector may be decreased.
The amount of the binder ranges from 0.8 to 5 wt% based on a total weight of the negative active material layer. According to one embodiment, the amount of the binder ranges from 1 to 5 wt%. According to another embodiment, the amount of the binder ranges from 1 to 2 wt%. When the amount of the binder is less than 0.8 wt%, binder content is significantly low and adherence between a negative active material and a current collector is not sufficient. On the contrary, when it is more than 5 wt%, the amount of the negative active material is low and thus a high-capacity battery cannot be realized.
Herein, aqueous or non-aqueous binders may be used for the binder.
For the aqueous binder, at least one selected from the group consisting of styrene-butadiene rubber (SBR), polyvinylalcohol, carboxymethylcellulose, hydroxypropyl cellulose, diacetyl cellulose, and mixtures thereof may be used. Since the aqueous binder can be dispersed in water in the form of an emulsion, it does not have to use an organic solvent. Also, since it is highly adhesive, the amount of the binder to be used can be reduced and the amount of the negative active material can be increased. Therefore, it is advantageous in the manufacture of a high-capacity lithium battery. The aqueous binder is used together with water or an aqueous solvent of water and an alcohol solvent.
When an aqueous binder is used, a thickener may be added thereto to adjust the viscosity. The thickener may be at least one selected from the group consisting of carboxyl methyl cellulose, hydroxymethyl cellulose, hydroxy ethyl cellulose, hydroxy propyl cellulose, and combinations thereof. The amount of the thickener may range from 0.8 to 5 wt% based on the entire negative active material layer. According to one embodiment, the amount of the thickener may range from 1 to 5 wt% based on the entire negative active material layer. According to another embodiment, the amount of the thickener may range from 1 to 2 wt% based on the entire negative active material layer.
When the amount of the thickener is less than 0.8 wt%, there may be a problem that the negative active material may run during coating. When the amount of the thickener is more than 5 wt%, the viscosity of the negative active material becomes too high for coating and rather it functions as a resistance. Also, when the amount of the thickener is more than 5 wt%, the amount of the negative active material is reduced so that the produced battery may not have particularly high capacity.
Examples of the non-aqueous binder include at least one selected from the group consisting of polyvinylchloride, polyvinylpyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, and mixtures thereof. These binders are used along with non-aqueous solvents such as N-methyl-2-pyrrolidone (NMP), dimethylformamide, tetrahydrofuran, and mixtures thereof.
Any electrically conductive material may be used as a conductive agent unless it causes a chemical change. Examples of the conductive agent include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, a metal powder or a metal fiber including copper, nickel, aluminum, silver, and so on, a polyphenylene derivative, or combinations thereof.
The current collector may be selected from the group consisting of a copper foil, a nickel foil, a stainless steel foil, a titanium foil, a nickel foam, a copper foam, a polymer substrate coated with a conductive metal, and combinations thereof.
The positive electrode includes a positive active material that is capable of performing a reversible electrochemical oxidation and reduction and is a generally-used lithiated intercalation compound in a rechargeable lithium battery. The lithiated intercalation compound includes compounds of the following Formulas 3 to 26.

[Chemical Formula 3] Li_aA_1-bB_bD₂

wherein, in the above formula, 0.95 ≤ a ≤ 1.1 and 0 ≤ b ≤ 0.5.

[Chemical Formula 4] Li_aE_1-bB_bO_2-cF_c

wherein, in the above formula, 0.95 ≤ a ≤ 1.1, 0 ≤ b ≤ 0.5, and 0 ≤ c ≤ 0.05.

[Chemical Formula 5] LiE_2-bB_bO_4-cF_c

wherein, in the above formula, 0 ≤ b ≤ 0.5 and 0 ≤ c ≤ 0.05.

[Chemical Formula 6] Li_aNi_1-b-cCo_bB_cD_α

wherein, in the above formula, 0.95 ≤ a ≤ 1.1, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < α ≤ 2.

[Chemical Formula 7] Li_aNi_1-b-cCo_bB_cO_2-αF_α

wherein, in the above formula, 0.95 ≤ a ≤ 1.1, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < α < 2.

[Chemical Formula 8] Li_aNi_1-b-cCo_bB_cO_2-αF₂

wherein, in the above formula, 0.95 ≤ a ≤ 1.1, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < α < 2.

[Chemical Formula 9] Li_aNi_1-b-cMn_bB_cD_α

wherein, in the above formula, 0.95 ≤ a ≤ 1.1, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < α ≤ 2.

[Chemical Formula 10] Li_aNi_1-b-cMn_bB_cO_2-αF_α

wherein, in the above formula, 0.95 ≤ a ≤ 1.1, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < α < 2.

[Chemical Formula 11] Li_aNi_1-b-cMn_bB_cO_2-αF₂

wherein, in the above formula, 0.95 ≤ a ≤ 1.1, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < α < 2.

[Chemical Formula 12] Li_aNi_bE_cG_dO₂

wherein, in the above formula, 0.90 ≤ a ≤ 1.1, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.9, and 0.001 ≤ d ≤ 0.2.

[Chemical Formula 13] Li_aNi_bCo_cMn_dG_eO₂

wherein, in the above formula, 0.90 ≤ a ≤ 1.1, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5, 0 ≤ d ≤ 0.5, and 0.001 ≤ e ≤ 0.2.

[Chemical Formula 14] Li_aNiG_bO₂

wherein, in the above formula, 0.90 ≤ a ≤ 1.1 and 0.001 ≤ b ≤ 0.1.

[Chemical Formula 15] Li_aCoG_bO₂

wherein, in the above formula, 0.90 ≤ a ≤ 1.1 and 0.001 ≤ b ≤ 0.1.

[Chemical Formula 16] Li_aMnG_bO₂

wherein, in the above formula, 0.90 ≤ a ≤ 1.1 and 0.001 ≤ b ≤ 0.1.

[Chemical Formula 17] Li_aMn₂G_bO₄

wherein, in the above formula, 0.90 ≤ a ≤ 1.1 and 0.001 ≤ b ≤ 0.1.

[Chemical Formula 18] QO₂

[Chemical Formula 19] QS₂

[Chemical Formula 20] LiQS₂

[Chemical Formula 21] V₂O₅

[Chemical Formula 22] LiV₂O₅

[Chemical Formula 23] LiIO₂

[Chemical Formula 24] LiNiVO₄

[Chemical Formula 25] Li_3-fJ₂(PO₄)₃ (0 ≤ f ≤ 3)

[Chemical Formula 26] Li_3-fFe₂(PO₄)₃ (0 ≤ f ≤ 2)
In the above Chemical Formulas 3 to 26, A is selected from the group consisting of Ni, Co, Mn, and combinations thereof; B is selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, and combinations thereof; D is selected from the group consisting of O, F, S, P, and combinations thereof; E is selected from the group consisting of Co, Mn and combinations thereof; F is selected from the group consisting of F, S, P, and combinations thereof; G is selected from the group consisting of Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, a lanthanide element, and combinations thereof, Q is selected from the group consisting of Ti, Mo, Mn, and combinations thereof; I is selected from the group consisting of Cr, V, Fe, Sc, Y, and combinations thereof; and J is selected from the group consisting of V, Cr, Mn, Co, Ni, Cu, and combinations thereof.
The electrolyte includes a non-aqueous organic solvent and a lithium salt.
The lithium salt is dissolved in the non-aqueous organic solvent to supply lithium ions in the battery. It may operate a basic operation of a rechargeable lithium battery, and it facilitates transmission of lithium ions between positive and negative electrodes. Non-limiting examples of the lithium salt include at least one supporting electrolyte salt selected from the group consisting of LiPF₆, LiBF₄, LiSbF₆, LiAsF₆, LiCF₃SO₃, LiN(SO₂C₂F₅)₂, LiN (CF₃SO₂)₂, LiC₄F₉SO₃, LiClO₄, LiAlO₂, LiAlCl₄, LiN(C_xF_2x+1SO₂)(C_yF_2y+1SO₂) (where x and y are natural numbers), LiCl, LiI, and lithium bisoxalate borate. The lithium salt may be used at a 0.1 to 2.0M concentration. When the lithium salt concentration is less than 0.1M, electrolyte performance may be deteriorated due to low electrolyte conductivity, whereas when it is more than 2.0M, lithium ion mobility may be reduced due to an increase of electrolyte viscosity.
The non-aqueous organic solvent acts as a medium for transmitting ions taking part in the electrochemical reaction of the battery. The non-aqueous organic solvent may include, but is not limited to, benzene, toluene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4-triiodobenzene, fluorotoluene, 1,2-difluorotoluene, 1,3-difluorotoluene, 1,4-difluorotoluene, 1,2,3-trifluorotoluene, 1,2,4-trifluorotoluene, chlorotoluene, 1,2-dichlorotoluene, 1,3-dichlorotoluene, 1,4-dichlorotoluene, 1,2,3-trichlorotoluene, 1,2,4-trichlorotoluene, iodotoluene, 1,2-diiodotoluene, 1,3-diiodotoluene, 1,4-diiodotoluene, 1,2,3-triiodotoluene, 1,2,4-triiodotoluene, R-CN (wherein R is a C2 to C50 linear, branched, or cyclic hydrocarbon, a double bond, an aromatic ring, or an ether bond), dimethylformamide, dimethylacetate, xylene, cyclohexane, tetrahydrofuran, 2-methyltetrahydrofuran, cyclohexanone, ethanol, isopropyl alcohol, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, methylpropyl carbonate, propyl carbonate, methyl propionate, ethyl propionate, methyl acetate, ethyl acetate, propyl acetate, dimethoxyethane, 1,3-dioxolan, diglyme, tetraglyme, ethylene carbonate, propylene carbonate, γ-butyrolactone, sulfolane, valerolactone, decanolide, and mevalolactone. The non-aqueous organic solvent may be used singularly or in a mixture. When the organic solvent is used in a mixture, a mixing ratio can be controlled in accordance with a desirable cell performance.
FIGURE 2 shows a rechargeable lithium battery having the above-mentioned structure according to an embodiment. Referring to FIGURE 2, the rechargeable lithium battery 3 is composed of an electrode assembly 4 including a positive electrode 5, a negative electrode 6, a separator 7 interposed between the positive electrode 5 and the negative electrode 6 which is positioned in a battery case 8. The upper part of the cell case is sealed with a cap plate 11 and a gasket 12. The rechargeable lithium battery according to the present embodiment is not limited to the above-mentioned shape, and may be shaped into a prismatic shape, a pouch, and so on.
The rechargeable lithium battery generally includes a positive electrode, a negative electrode, and an electrolyte. The battery may further include a separator as needed. The separator may include any material used in conventional lithium secondary batteries. Non-limiting examples of suitable separator materials include polyethylene, polypropylene, polyvinylidene fluoride, and multi-layers thereof such as a polyethylene/polypropylene double-layered separator, a polyethylene/polypropylene/polyethylene three-layered separator, and a polypropylene/polyethylene/polypropylene three-layered separator.
The following examples illustrate the present invention in more detail. However, it is understood that the present invention is not limited by these examples.

Example 1

1 g of silicon (10 mm) as a core material and 100 mL of ethanol were added into a reactor and uniformly dispersed. Then, 0.2 M aqueous ammonia prepared by mixing ammonia and water in a volume ratio of 29 : 71 was added to the dispersion. They were then uniformly mixed to prepare a core liquid.
On the other hand, a precursor liquid was prepared by adding 10 parts by weight of a compound represented by the following Formula 2a based on 100 parts by weight of the core material to 1 mL of ethanol and 1 mL of water.
The prepared precursor liquid was rapidly added to the core liquid to perform a hydrolysis and condensation reaction.
Next, the reaction solution was heated at 60 °C to volatilize ethanol, and then heat-treated at 450 °C to prepare a negative active material including a 8 nm-thick coating layer on the surface of silicon. The coating layer included as a core Si-O- was bounded with the core material, and a p-methyl phenyl group was positioned on a Si side chain that was not bonded with the core material.

Example 2

A negative active material was prepared to have a 12 nm-thick coating layer on the surface of the silicon according to the same method as in Example 1, except that 30 parts by weight of an organic-inorganic hybrid precursor was used based on 100 parts by weight of a core material.

Example 3

A negative active material was prepared to have a 19 nm-thick coating layer on the surface of the silicon according to the same method as in Example 1, except that 50 parts by weight of an organic-inorganic hybrid precursor was used based on 100 parts by weight of a core material.

Example 4

A negative active material was prepared to have a 9 nm-thick coating layer according to the same method as in Example 1, except that Li_1.1Ti_0.1V_0.9O₂ (10 mm) was used as a core material instead of silicon.

Example 5

A negative active material was prepared to have an 11 nm-thick coating layer according to the same method as in Example 4, except that 30 parts by weight of an organic-inorganic hybrid precursor was used based on 100 parts by weight of a core material.

Example 6

A negative active material was prepared to have a 20 nm-thick coating layer according to the same method as in Example 4, except that 50 parts by weight of an organic-inorganic hybrid precursor was used based on 100 parts by weight of a core material.

Comparative Example 1

Silicon was used as a negative active material.

Comparative Example 2

Li_1.1Ti_0.1V_0.9O₂ was used as a negative active material.

Experimental Example 1

The negative active material prepared according to the Example 1 was examined regarding structure of the coating layer by measuring FT-IR (Fourier Transform Infrared Spectroscopy) spectra. The results are shown in FIGURE 3.
FIGURE 3 showed FT-IR spectra of the negative active material prepared according to Example 1.
Referring to FIGURE 3, it had a Si-O peak around 1110 cm^-1. This means that the coating layer on the surface of negative active material prepared according to Example 1 had a -O-Si-O reticular structure formed from an organic-inorganic hybrid precursor.

Fabrication of a battery cell

A lithium cobalt oxide (LiCoO₂) positive active material and carbon black as a conductive agent were mixed to prepare a mixture. Next, a polyvinylidene fluoride binder was dissolved in an N-methyl-2-pyrrolidone solvent to prepare a binder solution. Then, the mixture was added to the binder solution to prepare a positive active material slurry.
The prepared positive active material slurry was coated to be 20µm thick on an aluminum foil in a doctor blade method, dried at 120 °C for 10 hours under a vacuum atmosphere to volatilize N-methyl-2-pyrrolidone, and pressed to fabricate a positive electrode.
Likewise, the negative active materials prepared according to Examples 1 to 6 and carbon black conductive agents were added to an N-methylpyrrolidone solution, in which a polyvinylidene fluoride binder was dissolved, to prepare negative active material slurries.
The prepared negative active material slurries were respectively coated to be 12µm thick on a copper foil in a doctor blade method, dried at 120 °C for 10 hours under a vacuum atmosphere to volatilize N-methyl-2-pyrrolidone, and pressed to fabricate negative electrodes.
Then, rechargeable lithium battery cells were fabricated using the positive and negative electrodes and a polyolefin (polyethylene and polypropylene) separator.

Experimental Example 2

The rechargeable lithium battery cells including the negative active materials according to the Examples 1 to 6 and Comparative Examples 1 and 2 were charged up to 4.2 V and discharged down to 2.75 V at 0.2C. Then, their coulomb efficiency was measured to estimate their initial reversible efficiency. The results are shown in the following Table 1. Table 1

Coulomb Efficiency

Example 1 80.5 %

Example 2 81.8 %

Example 3 77.0%

Example 4 91.8%

Example 5 90.0%

Example 6 87.5%

Comparative Example 1 72.0%

Comparative Example 2 86.0%
As shown in the Table 1, the battery cells according to Examples 1 to 3 of the present invention had high coulomb efficiency compared with the battery cell according to Comparative Example 1. The same results were obtained when the battery cells according to Examples 4 to 6 were compared with that of Comparative Example 2. As a result, a negative active material of the present invention includes an inorganic oxide coating layer on the surface, and can thereby minimize interface reactivity between a negative electrode and an electrolyte during the operation of a battery cell, improving charge and discharge efficiency and cycle-life characteristic of a rechargeable lithium battery cell.

Experimental Example 3

The rechargeable lithium battery cells including the negative active materials according to the Examples 2 and 4 and Comparative Examples 1 and 2 were charged up to 4.2 V at 0.2C and discharged up to 3.0 V at 0.2C. The charge and discharge was 50 times repeated. The results are shown in the FIGURE 4. Herein, capacity retention after 50th charge and discharge means the ratio of the 50th charge and discharge capacity verse the first charge and discharge capacity.
FIGURE 4 is a graph showing capacity retention of the cells of Examples 2 and 4 and Comparative Examples 1 and 2 during 50 charges and discharges.
Referring to FIGURE 4, the battery cells according to Examples 2 and 4 of the present invention, which included a negative active material including a coating layeron the surface after 50 charges and discharges, turned out to have a lower decreasing capacity rate than the ones according to Comparative Examples 1 and 2.
Therefore, a negative active material for a rechargeable lithium battery according to the present invention can be applied along with an aqueous binder, and improve high capacity, good cycle-life, and particularly high capacity during charge and discharge at a high rate.
While this invention has been described in connection with the foregoing exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

Claims

A negative active material for a rechargeable lithium battery, comprising:
a core comprising an active material capable of performing reversible electrochemical oxidation and reduction; and
a coating layer on a surface of the core, the coating layer having a reticular structure including -O-M-O- wherein M is selected from the group consisting of Si, Ti, Zr, Al, and combinations thereof, and an organic functional group linked to M as a side chain, the organic functional group selected from the group consisting of an alkyl group, a haloalkyl group, a substituted or unsubstituted aryl group, and combinations thereof.
The negative active material of claim 1, wherein the organic functional group is an aryl group substituted by at least one functional group selected from the group consisting of an alkyl group and a haloalkyl group.
The negative active material of claim 1, wherein the organic functional group is selected from the group consisting of a C1 to C10 alkyl group, a C1 to C10 haloalkyl group, a C6 to C12 aryl group, a C6 to C12 aryl group substituted by at least one C1 to C10 alkyl group, a C6 to C12 aryl group substituted by at least one C1 to C10 haloalkyl group, and combinations thereof.
The negative active material of claim 3, wherein the organic functional group is an aryl group selected from the group consisting of benzyl, phenyl, and tolyl.
The negative active material of any one of claims 1 to 4, wherein the coating layer has a thickness of 20 nm or less.
The negative active material of any one of the preceding claims, wherein the active material is selected from the group consisting of a material capable of reversibly intercalating and deintercalating lithium ions, lithium metal, a lithium-containing alloy, and a material capable of reversibly forming a lithium-containing compound by reacting with lithium ions.
The negative active material of claim 6, wherein the active material is selected from the group consisting of crystalline carbon, amorphous carbon, Si, silicon oxide, Sn, tin oxide, a tin alloy composite, a transition element oxide, a lithium metal nitride, lithium vanadium oxide, and a lithium-containing alloy including at least one metal selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, Fe and Sn.
The negative active material of claim 7, wherein the active material is a compound represented by Formula 1:

Li_xM'_yV_zO_2+d (1)

wherein 0.1≤x≤2.5, 0≤y≤0.5, 0.5≤z≤1.5, 0≤d≤0.5, and M' of Formula 1 is a metal selected from the group consisting of Al, Cr, Mo, Ti, W, Zr, and combinations thereof.
The negative active material of any one of the preceding claims, wherein the coating layer is comprised of a hydrolysis and condensation product of a compound represented by Formula 2:

R₁-M-(OR₂)_n (2)

wherein M of Formula 2 is selected from the group consisting of Si, Ti, Zr, and Al, R1 is the organic functional group, R2 is, in each case independently, a C1 to C7 alkyl group, and n is determined according to the valence of M.
A method of preparing a negative active material for a rechargeable lithium battery, comprising:
preparing a core liquid by mixing an active material capable of performing reversible electrochemical oxidation and reduction, an organic solvent, a base, and water;

preparing a precursor liquid comprising an organic-inorganic hybrid precursor represented by Formula 2, an organic solvent, and water;

R₁-M-(OR₂)_n (2)

wherein M of Formula 2 is selected from the group consisting of Si, Ti, Zr, and Al, R1 is selected from the group consisting of an alkyl group, a haloalkyl group, a substituted or unsubstituted aryl group, and combinations thereof, R2 is, in each case independently, a C1 to C7 alkyl group, and n is determined according to the valence of M;

mixing the core liquid and the precursor liquid; and

volatilizing the organic solvent and heat-treating the mixed core liquid and precursor liquid to obtain the negative active material.
The method of claim 10, wherein the organic-inorganic hybrid precursor is represented by Formula 2a:
The method of claim 10, wherein the organic functional group is an aryl group substituted by at least one functional group selected from the group consisting of an alkyl group and a haloalkyl group.
The method of claim 10, wherein R1 is selected from the group consisting of a C1 to C10 alkyl group, a C1 to C10 haloalkyl group, a C6 to C12 aryl group, a C6 to C12 aryl group substituted by at least one C1 to C10 alkyl group, a C6 to C12 aryl group substituted by at least one C1 to C10 haloalkyl group, and combinations thereof, and R2 is a C1 to C5 alkyl group.
The method of any one of claims 10 to 13, wherein the base is aqueous ammonia.
The method of any one of claims 10 to 14, wherein the organic-inorganic hybrid precursor is used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the active material.
The method of any one of claims 10 to 15, wherein the active material is used in an amount of 1 to 10 g based on 1,000 ml of the organic solvents in the mixture of the core liquid and the precursor liquid, the base is used at a concentration of 0.05 to 1 M, and the water is used at a concentration of 10 to 20 M in the mixture of the core liquid and the precursor liquid.
The method of any one of claims 10 to 16, wherein the active material is a material selected from the group consisting of a material capable of reversibly intercalating and deintercalating lithium ions, a lithium metal, a lithium-containing alloy, and a material being capable of reversibly forming a lithium-containing compound by reacting with lithium ions.
The method of claim 17, wherein the active material is selected from the group consisting of crystalline carbon; amorphous carbon; Si, silicon oxide, Sn, tin oxide, a tin alloy composite, a transition element oxide, a lithium metal nitride, lithium vanadium oxide, and a lithium-containing alloy including at least one metal selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, Fe and Sn.
The method of claims 17 or 18, wherein the active material is a compound represented by Formula 1:

Li_xM'_yV_zO_2+d (1)

wherein 0.1 ≤ x ≤ 2.5, 0 ≤ y ≤ 0.5, 0.5 ≤ z ≤ 1.5, 0 ≤ d ≤ 0.5, and M' of Formula 1 is a metal selected from the group consisting of Al, Cr, Mo, Ti, W, Zr, and combinations thereof.
A rechargeable lithium battery comprising:
a negative electrode comprising:

a negative active material comprising:

a core comprising an active material capable of performing reversible electrochemical oxidation and reduction; and

a coating layer on a surface of the core, the coating layer having a reticular structure including -O-M-O- wherein M is selected from the group consisting of Si, Ti, Zr, Al, and combinations thereof, and an organic functional group linked to M as a side chain, the organic functional group selected from the group consisting of an alkyl group, a haloalkyl group, a substituted or unsubstituted aryl group, and combinations thereof;
a positive electrode comprising a positive active material; and
an electrolyte.
The rechargeable lithium battery of claim 20, wherein the organic functional group is an aryl group substituted by at least one functional group selected from the group consisting of an alkyl group and a haloalkyl group.
The rechargeable lithium battery of claims 20 or 21, wherein the coating layer has a thickness of 20 nm or less.
The rechargeable lithium battery of claims 20, 21 or 22, wherein the active material is a material selected from the group consisting of a material capable of reversibly intercalating and deintercalating lithium ions, lithium metal, a lithium-containing alloy, a material capable of reversibly forming a lithium-containing compound by reacting with lithium ions.
The rechargeable lithium battery of claim 23, wherein the active material is selected from the group consisting of crystalline carbon; amorphous carbon; Si, silicon oxide, Sn, tin oxide, a tin alloy composite, a transition element oxide, a lithium metal nitride, lithium vanadium oxide, and a lithium-containing alloy including at least one metal selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, Fe and Sn.
The rechargeable lithium battery of claims 23 or 24, wherein the active material is a compound represented by Formula 1:

Li_xM'_yV_zO_2+d (1)

wherein 0.1 ≤ x ≤ 2.5, 0 ≤ y ≤ 0.5, 0.5 ≤ z ≤ 1.5, 0 ≤ d ≤ 0.5, and M' of Formula 1 is a metal selected from the group consisting of Al, Cr, Mo, Ti, W, Zr, and combinations thereof.
Use of a negative active material as claimed in any one of claims 1 to 9 for an electrode of a rechargeable lithium battery.